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Hyperbranched polymers as scaffolds for multifunctional reversible addition–fragmentation chain-transfer agents: A route to polystyrene-core-polyesters and polystyrene-block-poly(butyl acrylate)-core-polyesters

Authors

  • Martin Jesberger,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, UNSW Sydney NSW 2052, Australia
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  • Leonie Barner,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, UNSW Sydney NSW 2052, Australia
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  • Martina H. Stenzel,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, UNSW Sydney NSW 2052, Australia
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  • Eva Malmström,

    1. Fibre and Polymer Technology, Royal Institute of Technology, Teknikringen 56-58, SE-100 44 Stockholm, Sweden
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  • Thomas P. Davis,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, UNSW Sydney NSW 2052, Australia
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  • Christopher Barner-Kowollik

    Corresponding author
    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, UNSW Sydney NSW 2052, Australia
    • Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, UNSW Sydney NSW 2052, Australia
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Abstract

Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition–fragmentation chain-transfer (RAFT) agents. The polyester-core-based RAFT agents were subsequently employed to synthesize star polymers of n-butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free-radical process. Although the polyester-core-based RAFT agent mediated polymerization of n-butyl acrylate displayed a linear evolution of the number-average molecular weight (Mn) up to high monomer conversions (>70%) and molecular weights [Mn > 140,000 g mol−1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene-based system reached a maximum molecular weight at low conversions (≈30%, Mn = 45,500 g mol−1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n-butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene-based star polymers were successfully cast into highly regular honeycomb-structured microarrays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3847–3861, 2003

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